Cigarettes and cigarette components containing nanostructured fibril materials

ABSTRACT

Cigarettes and cigarette components such as tobacco cut filler and cigarette paper, and methods for making cigarette components are provided that comprise nanostructured fibrils. The nanostructured fibrils, which can be formed and deposited in situ on tobacco cut filler and/or cigarette paper by laser vaporization controlled condensation or chemical reaction, are capable of acting as an oxidant for the conversion of carbon monoxide carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide. Cigarettes are provided that comprise tobacco cut filler and cigarette paper, wherein nanostructured fibrils are deposited on, or incorporated in, at least one of the tobacco cut filler and cigarette paper.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 10/972,203 entitled CIGARETTES AND CIGARETTE COMPONENTS CONTAININGNANOSTRUCTURED FIBRIL MATERIALS, filed on Oct. 25, 2004 now U.S. Pat.No. 7,509,961 which claims priority under 35 U.S.C. §119 to U.S.Provisional Application No. 60/514,526 entitled CIGARETTES AND CIGARETTECOMPONENTS CONTAINING NANOSTRUCTURED FIBRIL MATERIALS, filed Oct. 27,2003, the entire contents of each is hereby incorporated by reference.

BACKGROUND

Various methods for reducing the amount of carbon monoxide in themainstream smoke of a cigarette during smoking have been proposed.

Despite the developments to date, there remains an interest in improvedand more efficient methods and compositions for reducing the amount ofcarbon monoxide in the mainstream smoke of a cigarette during smoking.

SUMMARY

Nanostructured fibrils can be formed and deposited directly on cigarettecomponents such as tobacco cut filler and cigarette paper. According toan embodiment, the nanostructured fibrils can be formed and deposited insitu directly on tobacco cut filler and/or cigarette paper using laservaporization controlled condensation (LVCC). According to a furtherembodiment, the nanostructured fibrils can be formed (e.g., by LVCC orother suitable techniques) and then deposited on and/or incorporated ina component of a cigarette such as tobacco cut filler and/or cigarettepaper.

The nanostructured fibrils can be formed by laser vaporizationcontrolled condensation. The method comprises supporting a substrate ina chamber having a target and first and second electrodes; applying anelectrical bias between the electrodes to form electrical field linesbetween the electrodes; and bombarding the target with a high energysource to form nanoscale particles from the target material thatagglomerate with each other along the direction of the electrical fieldlines to form nanostructured fibrils on the substrate. The substrate cancomprise tobacco cut filler and/or cigarette paper, or the substrate cancomprise the first or second electrode.

The first and second electrodes, which are preferably plates arrangedparallel to one another, can be maintained at a temperature during thebombardment of from about −196° C. to 100° C. Furthermore, a temperaturegradient between the plates of greater than about 100° C. can bemaintained during the bombardment. The first plate, on which the fibrilscan be deposited, can be located at a distance of from about 2 to 20 cmfrom the target. An electrical bias of less than about 100 V/cm, e.g.,about 10, 20, 30, 40, 50, 60, 70, 80 or 90 V/cm is preferably appliedbetween the first and second plates.

According to a preferred embodiment, the chamber comprises a vacuumchamber such as a diffusion cloud chamber. Laser bombardment of thetarget can be carried out in an inert atmosphere or an atmospherecomprising a reactive gas. For example, bombardment of the target can beperformed in an atmosphere comprising an oxygen-containing gas.Preferred oxygen-containing gases include air, oxygen and water vapor.Bombardment of the target can be carried out at a chamber pressure ofgreater than about 1×10⁻⁴ Torr, preferably at about atmosphericpressure.

According to a preferred embodiment the target comprises manganese, ironand/or copper and can be bombarded with a Nd-YAG laser, ion laser, diodearray laser or pulsed excimer laser to form nanostructured fibrils thatcomprise manganese, iron and/or copper (e.g., nanostructured fibrilsthat comprise manganese, iron and/or copper metal, and/or compounds suchas oxides or oxyhydroxides of manganese, iron and/or copper).

The nanostructured fibrils can have a dimension (e.g., width ordiameter) of less than about 500 nm, more preferably less than about 100nm, most preferably less than about 50 nm. The nanostructured fibrilscan have an aspect ratio of length to width of greater than about 10:1,e.g., greater than about 1,000:1 or greater than about 1,000,000:1. Thefibrils preferably comprise thread-like fibers or filaments.

The nanostructured fibrils, which can have a crystalline or amorphousstructure, preferably comprise a metal compound such as a metal oxide,metal oxyhydroxide or mixed metal oxide such as manganese oxide, ironoxide, copper oxide or mixtures thereof. Mixtures of nanostructuredfibrils having different compositions as well as alloyed nanostructuredfibrils can be formed by simultaneous or sequential evaporation ofseveral different targets and/or targets comprising more than onemetallic element.

According to a preferred embodiment, a cigarette can be formed bydepositing nanostructured fibrils on tobacco cut filler and/or cigarettepaper, providing the tobacco cut filler to a cigarette making machine toform a tobacco column; and placing the cigarette paper around thetobacco column to form a tobacco rod of a cigarette. The nanostructuredfibrils can be deposited on tobacco cut filler to give preferably lessthan about 10% by weight of nanostructured fibrils on the tobacco cutfiller. As mentioned above, the nanostructured fibrils can be formeddirectly on the tobacco cut filler or cigarette paper, or previouslyformed nanostructured fibrils can be deposited on and/or incorporated inthe tobacco cut filler or cigarette paper. For example, thenanostructured fibrils can be formed and then deposited on the tobaccocut filler or cigarette paper by dusting.

According to a further embodiment, nanostructured fibrils can be formeddirectly on a component of a cigarette by forming a metal oxide from asolution comprising a metal salt and sodium hydroxide; drying the metaloxide; and combining the metal oxide with the cigarette component,wherein the metal oxide reacts with moisture in the cigarette componentto form nanostructured fibrils.

The nanostructured fibrils are capable of acting as an oxidant for theconversion of carbon monoxide to carbon dioxide and/or as a catalyst forthe conversion of carbon monoxide to carbon dioxide. The nanostructuredfibrils can be incorporated into a cigarette in an amount effective toreduce the ratio in mainstream tobacco smoke of carbon monoxide to totalparticulate matter by at least 10%, e.g., at least 25%.

Further embodiments provide cigarettes comprising nanostructuredfibrils, wherein the cigarettes comprise tobacco cut filler andcigarette paper and the nanostructured fibrils are deposited on orincorporated in at least one of the tobacco cut filler and cigarettepaper.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of an experimental set up for the formation ofnanostructured fibrils by the LVCC method.

FIG. 2 shows an SEM image of nanostructured fibrils of MnOOH formed byoxidation of manganese oxide at room temperature.

FIGS. 3A and 3B shows SEM images of nanostructured fibrils of MnOOHformed by oxidation of manganese oxide at 44° C. and 92° C.,respectively.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Provided are cigarettes and cigarette components such as tobacco cutfiller and cigarette paper that comprise nanostructured fibrils usefulfor reducing CO in cigarette smoke. According to a preferred method, thenanostructured fibrils can be formed and deposited in situ directly on acigarette component using laser vaporization controlled condensation(LVCC). The method comprises supporting a target and a substrate in achamber having first and second electrodes; applying an electrical biasto the first electrode with respect to the second electrode to formelectrical field lines between the electrodes; and bombarding the targetwith a high energy source to form nanoscale particles from the targetmaterial that agglomerate along the direction of the electrical fieldlines to form nanostructured fibrils on the substrate. According to afurther embodiment, the nanostructured fibrils can be formed by LVCC andlater deposited on and/or incorporated in one or more components of acigarette. According to yet a further preferred method, nanostructuredfibrils can be formed by precipitating a metal salt under basicconditions to produce a metal oxide, which is then converted tonanostructured oxide or oxyhydroxide fibrils upon exposure to warm,moist air.

A further embodiment relates to a method of making a cigarette,comprising depositing nanostructured fibrils on at least one of tobaccocut filler and cigarette paper; providing the tobacco cut filler to acigarette making machine to form a tobacco column; and placing thecigarette paper around the tobacco column to form a tobacco rod of acigarette.

The nanostructured fibrils, which are capable of acting as an oxidantfor the conversion of carbon monoxide to carbon dioxide and/or as acatalyst for the conversion of carbon monoxide to carbon dioxide, canreduce the amount of carbon monoxide in mainstream smoke during smoking.Because of their two-dimensional shape (e.g., fibrous shape), thenanostructured fibrils can exhibit better adhesion to tobacco cut fillerand/or cigarette paper than free flowing one-dimensional nanoscaleparticles.

With laser vaporization controlled condensation, material from a source(i.e., target) is removed from the target by physical erosion anddeposited on a surface of a substrate. The target is formed of (orcoated with) a consumable material to be removed and deposited, i.e.,target material.

Laser vaporization controlled condensation is preferably implemented byimpinging the surface of a target with a high energy source such as alaser beam in a controlled pressure gas atmosphere. Energy from thelaser beam, which is preferably rastered across the surface of thetarget, can cause sputtering of the target material (i.e., charged andneutral species of target material can be ejected from target). Thegrowth of nanostructured fibrils of intermetallic compounds such asFeAl, Ti₃Al, NiAl and CuZn using LVCC is disclosed by El-Shall et al. inJ Phys. Chem. B 2003, 107, 2882-2886.

If the density of the ejected species is sufficiently low, and theirrelative velocities sufficiently high, charged and neutral species fromthe target travel through the gas until they impact the surface of asubstrate where they can coalesce into nanoscale particles that formnanostructured fibrils under the force of the applied electric field. Ifthe density of the ejected species is sufficiently high, and theirrelative velocities sufficiently small, species ejected from the targetcan aggregate in the gas phase into nanoscale particles that formnanostructured fibrils in the gas phase under the force of the appliedelectric field, which can then deposit on a substrate. Fibril growth iscaused by particle assembly initiating at one of the chamber electrodesand extending under the influence of the applied field towards theopposite electrode.

Without wishing to be bound by theory, at a chamber pressure lower thanabout 10⁻⁴ Torr the mean free path of ablated species is sufficientlylong that ablated species arrive at the substrate without undergoingsignificant gas phase collisions. Thus, at lower pressures, ablatedmaterial can deposit on the substrate as individual species, which maydiffuse and coalesce with each other to form nanoscale fibrils afteralighting on the substrate surface. At a higher pressures, such aspressures above about 10⁻⁴ Torr, the collision frequency in the gasphase of ablated species is significantly higher and nucleation andgrowth of the ablated species to form nanostructured fibrils can occurin the gas phase before alighting on the substrate surface. Thus, athigher pressures, ablated material can form nanoscale particles in thegas phase, which can agglomerate to form nanostructured fibrils underthe force of an applied electric field.

Both charged and neutral species that are ejected from a target canexperience electrophoretic forces under an applied electric field. Forexample, in a non-uniform electric field, neutral species can exhibit atranslational motion known as dielectrophoresis. Thus, nanostructuredfibrils can be assembled from both neutral and charged species under theforce of an applied electric field. Depending on parameters such as thechamber pressure, the temperature and voltage gradients between theelectrodes, laser energy and choice of target material, nanostructuredfibrils can be formed from particles in the gas phase and/or fromparticles that have alighted on the surface of a substrate.

A method of depositing nanostructured fibrils via laser vaporizationcontrolled condensation is provided in conjunction with the exemplaryapparatus depicted in FIG. 1. Apparatus 20 includes a diffusion cloudchamber 21 having an optional throttle valve 22 that separates thechamber 21 from an optional vacuum pump (not shown). A target 23, suchas a pressed powder target of iron oxide, is mounted on an upperelectrode plate 26 of the chamber 21. Lower electrode plate 28 canfunction as a substrate for the deposition of nanostructured fibrils or,alternatively, an optional substrate material such as tobacco cut filleror cigarette paper, can be positioned on the lower electrode plate 28.Upper and lower electrode plates, which can be separated by aninsulating ring such as a quartz ring, can be formed of a conductivematerial, such as stainless steel. The quartz ring can have a height offrom about 2 to 20 cm, preferably about 5 cm.

During the formation of nanostructured fibrils, the upper electrodeplate 26 is preferably maintained at a temperature greater than thetemperature of the lower electrode plate 28. For example, the upperelectrode plate can be maintained at a temperature of from about 20 to100° C., and the lower electrode plate can be maintained at atemperature of from about −196 to 30° C. The temperature gradientbetween the top and bottom electrode plates results in a steadyconvection current, which can be enhanced by increasing the chamberpressure (e.g. to pressures greater than about 10³ torr). Thetemperature gradient can be maintained between the upper and lowerelectrode plates during the deposition by flowing a cooling liquid suchas chilled water or liquid nitrogen through lower electrode plate and/orflowing a heating liquid such as hot oil through the upper electrodeplate.

Referring still to FIG. 1, the reactor chamber 21 contains conduits 34and 35 for introducing various gases. For example, helium could beintroduced through conduit 34 and, optionally, oxygen through conduit35. Gases are introduced into the chamber by first passing them throughseparate flow controllers to provide a total pressure of gasses in thechamber of greater than about 10⁻⁴ Torr, preferably about 1 to 10³ Torr.

Nanostructured fibrils may be formed and deposited on a substrate usingan ablation process, wherein a suitable high energy source such as alaser is aimed at a target under conditions sufficient to release (i.e.,ablate) individual particles from the target. Lasers include, but arenot limited to, Nd-YAG lasers, ion lasers, diode array lasers and pulsedexcimer lasers. For example, nanostructured fibrils can be generated bypulsed laser vaporization using the second harmonic (532 nm) of a Nd:YAGlaser (e.g., about 50-70 mJ/pulse, 10 nanosecond pulse).

Advantageously, ablation such as laser ablation can be performed at orabove atmospheric pressure without the need for vacuum equipment. Thus,the nanostructured fibrils may be simultaneously formed and deposited ona substrate that is maintained at or near ambient temperature andatmospheric pressure during the deposition process.

An apparatus for ablative processing includes a chamber in which atarget material is placed. An external energy source, such as a pulsedexcimer laser, enters the chamber through a window, preferably quartz,and interacts with target. Alternatively, the energy source can beinternal, i.e., positioned inside the chamber.

In an ablative process, a region of the target absorbs incident energyfrom the energy source. This absorption and subsequent heating of thetarget causes target material to ablate from the surface of the targetinto a plume of ionic, atomic and nanometer-scale particles. Thesubstrate material may be supported on a substrate holder or, because alaser ablation process can be carried out at atmospheric pressure,passed through the chamber on a moving substrate holder such as aconveyor belt operated continuously or discontinuously to provide adesired amount of deposited nanostructured fibrils on the substratematerial.

If desired, in place of the laser, the high energy source can be an ionbeam from an accelerator, ion separator or an ion gun. An ion beam maycomprise inert gas ions such as neon, argon, krypton or xenon. Argon ispreferred because it can provide a good sputter yield and is relativelyinexpensive. The energy of the bombarding inert gas ion beam can bevaried, but should be chosen to provide a sufficient sputtering yield.The ion beam can be scanned across the surface of the target material inorder to improve the uniformity of target wear.

An electrical bias is applied between first and second electrode plates,which can form the upper and lower walls of the chamber. Thenanostructured fibrils can be deposited directly on the lower electrodeplate, which is preferably supported at a distance of from about 2 to 20cm from the target. Alternatively, the tobacco cut filler or cigarettepaper can be supported on the lower electrode plate and thenanostructured fibrils can be deposited directly on the tobacco cutfiller or cigarette paper. Under the force of the electric field thatforms between the two electrode plates, nanoscale particles that formfrom laser ablation of the target material can agglomerate together toform the nanostructured fibrils.

The introduction of reactive gases into the chamber during the ablationprocess allows material sputtered from the target to react and/orcombine with such gases to obtain compound nanostructured fibrils. Thus,during reactive laser vaporization controlled condensation, the gaswithin the chamber includes a small proportion of a reactive gas, suchas air, oxygen, water vapor, etc., which reacts with the atoms of thetarget material to form metal compound particles such as oxide nanoscaleparticles that can agglomerate under an applied electric field to formcompound nanostructured fibrils such as nanostructured oxide fibrils.For example, nanostructured iron oxide fibrils may be deposited byablating an iron target in the presence of an oxygen-containing gas(e.g., oxygen, air and/or water vapor).

Compound nanostructured fibrils can also be deposited via ablation ofthe corresponding compound (e.g., oxide) target. For example,nanostructured iron oxide fibrils may be deposited by ablating an ironoxide target.

The microstructure and composition of the nanostructured fibrils can becontrolled using LVCC. Density, phase distribution and the extent andmorphology of crystalline (versus amorphous) phases can be controlled byvarying, for example, the deposition pressure, reactive gas flow, laserenergy, substrate temperature and applied bias.

The nanostructured fibrils can comprise B, Ti, V, Cr, Fe, Co, Ni, Cu,Zn, Ge, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Sn, Ce, Hf, Ta, W, Re, Os, Ir,Pt, Au, as well as compounds such as oxides, oxyhydroxides and mixturesthereof. By way of example, the nanostructured fibrils can comprisemetallic fibrils such as Fe or Ni fibrils; intermetallic fibrils such asFeAl, Ti₃Al or NiAl fibrils; oxyhydroxide fibrils such as FeOOH or MnOOHfibrils; metal oxide fibrils such as Fe₂O₃, TiO₂, or Cu₂O fibrils, ormixtures thereof.

As discussed above, the substrate is typically placed proximate to thetarget such that it is in the path of the ablated target atoms and thetarget material is deposited on the surface of the substrate.

By regulating the deposition parameters, including background gas,pressure, substrate temperature and time, it is possible to preparetobacco cut filler and/or cigarette paper that comprise a loading anddistribution of nanostructured fibrils thereon effective to reduce theamount of carbon monoxide in mainstream smoke. According to anembodiment, the nanostructured fibrils can be formed and deposited insitu on the tobacco cut filler and/or cigarette paper. In an embodimentwhere the nanostructured fibrils are deposited directly on tobacco cutfiller and/or cigarette paper, the LVCC process is stopped when there isstill exposed substrate surface. That is, the ablation method does notbuild up a continuous layer but rather forms nanostructured fibrils thatare uniformly or non-uniformly distributed over the tobacco cut fillerand/or cigarette paper surface. During the processes of formation anddeposition, new fibrils form and existing fibrils can grow.

Advantageously, LVCC allows for dry, solvent-free, simultaneousformation and deposition of nanostructured fibrils directly on tobaccocut filler and/or cigarette paper under sterile conditions.

According to a further embodiment, the nanostructured fibrils can beformed by LVCC or other suitable methods and later deposited on orincorporated in the tobacco cut filler and/or cigarette paper.

In addition to LVCC, nanostructured fibrils can be formed byprecipitating a metal salt under basic conditions to produce a metaloxide, which is then converted to nanostructured oxide or oxyhydroxidefibrils upon exposure to warm, moist air. An oxide (e.g., hausmanite(Mn₃O₄)) can be prepared via precipitation of a metal salt (e.g.,manganese nitrate) using sodium hydroxide as a precipitation agent. Theoxide can comprise nanoscale or larger sized particles. Individual oxideparticles and/or irregularly shaped agglomerates of oxide particles canbe converted to nanostructured fibrils upon exposure to warm, moist air.The rate of formation of the fibrils is a function of temperature andmoisture. Preferably, the temperature to convert the oxide tonanostructured fibrils is greater than about room temperature,preferably between about 80° C. to 100° C., and the relative humidity isgreater than about 65%, preferably from about 90% to 100%. Once formed,the fibrils can be combined with tobacco cut filler and/or cigarettepaper, which can be incorporated into a cigarette. In an alternativeembodiment, an oxide can convert to nanostructured fibrils after theoxide has been incorporated in the tobacco cut filler or cigarettepaper. Oxide particles can react with moisture in the tobacco cut filleror cigarette paper to form nanostructured fibrils.

By way of example, a 0.1 M aqueous solution of sodium hydroxide wasadded under vigorous stirring to an aqueous solution of manganese (II)nitrate (99.98% purity) to adjust the solution pH to about 10. Thesolution temperature was about 65° C. The resulting slurry was aged forabout 1 hour, filtered, washed with dionized water, and then dried. Thedried filtrate comprised irregularly shaped agglomerates of hausmanite(Mn₃O₄). Fiber formation was observed by exposing the dried filtrate tooxidizing conditions. By exposing the dried filtrate to heated, humidair, the dried filtrate can restructure to a fibrous form of MnOOH.Manganese oxide can restructure to form fibrous manganese oxyhydroxideaccording to the following reaction pathway: 4 Mn₃O₄+6H₂O+O₂−12 MnOOH.

An SEM image of MnOOH fibrils formed by exposing the dried filtrate toroom temperature air having 60-65% relatively humidity for 45 days isshown in FIG. 2. The rate of conversion of the dried oxide filtrate tonanostructured oxide fibrils can be increased by increasing thetemperature and/or relative humidity of the oxidizing condition. An SEMimage of MnOOH fibrils formed by exposing the dried filtrate to 44° C.air and 92° C. air having 60-65% relatively humidity for 2.5 days isshown in FIGS. 3A and 3B, respectively.

Preferably, the nanostructured fibrils are deposited on or incorporatedin the tobacco cut filler and/or cigarette paper in an amount effectiveto reduce the ratio in mainstream smoke of carbon monoxide to totalparticulate matter (e.g., tar) by at least 10%, more preferably by atleast 25%. Preferably, the nanostructured fibrils comprise less thanabout 10% by weight of the tobacco cut filler, more preferably less thanabout 5% by weight of the tobacco cut filler.

“Smoking” of a cigarette means the heating or combustion of thecigarette to form smoke, which can be drawn through the cigarette.Generally, smoking of a cigarette involves lighting one end of thecigarette and, while the tobacco contained therein undergoes acombustion reaction, drawing the cigarette smoke through the month endof the cigarette. The cigarette may also be smoked by other means. Forexample, the cigarette may be smoked by heating the cigarette and/orheating using electrical heater means, as described in commonly-assignedU.S. Pat. No. 6,053,176; 5,934,289; 5,591,368 or 5,322,075.

The term “mainstream” smoke refers to the mixture of gases passing downthe tobacco rod and issuing through the filter end, i.e., the amount ofsmoke issuing or drawn from the mouth end of a cigarette during smokingof the cigarette.

In addition to the constituents in the tobacco, the temperature and theoxygen concentration are factors affecting the formation and reaction ofcarbon monoxide and carbon dioxide. The total amount of carbon monoxideformed during smoking comes from a combination of three main sources:thermal decomposition (about 30%), combustion (about 36%) and reductionof carbon dioxide with carbonized tobacco (at least 23%). Formation ofcarbon monoxide from thermal decomposition, which is largely controlledby chemical kinetics, starts at a temperature of about 180° C. andfinishes at about 1050° C. Formation of carbon monoxide and carbondioxide during combustion is controlled largely by the diffusion ofoxygen to the surface (k_(a)) and via a surface reaction (k_(b)). At250° C., k_(a) and k_(b), are about the same. At 400° C., the reactionbecomes diffusion controlled. Finally, the reduction of carbon dioxidewith carbonized tobacco or charcoal occurs at temperatures around 390°C. and above.

During smoking there are three distinct regions in a cigarette: thecombustion zone, the pyrolysis/distillation zone, and thecondensation/filtration zone. While not wishing to be bound by theory,it is believed that the nanostructured fibrils can target the variousreactions that occur in different regions of the cigarette duringsmoking.

First, the combustion zone is the burning zone of the cigarette producedduring smoking of the cigarette, usually at the lighted end of thecigarette. The temperature in the combustion zone ranges from about 700°C. to about 950° C., and the heating rate can be as high as 500°C./second. Because oxygen is being consumed in the combustion of tobaccoto produce carbon monoxide, carbon dioxide, water vapor and variousorganic compounds, the concentration of oxygen is low in the combustionzone. The low oxygen concentrations coupled with the high temperatureleads to the reduction of carbon dioxide to carbon monoxide by thecarbonized tobacco. In this region, the nanostructured fibrils canconvert carbon monoxide to carbon dioxide via both catalysis andoxidation mechanism. The combustion zone is highly exothermic and theheat generated is carried to the pyrolysis/distillation zone.

The pyrolysis zone is the region behind the combustion zone, where thetemperatures range from about 200° C. to about 600° C. The pyrolysiszone is where most of the carbon monoxide is produced. The majorreaction is the pyrolysis (i.e., the thermal degradation) of the tobaccothat produces carbon monoxide, carbon dioxide, smoke components andcharcoal using the heat generated in the combustion zone. There is someoxygen present in this region, and thus the nanostructured fibrils mayact as a catalyst for the oxidation of carbon monoxide to carbondioxide. The catalytic reaction begins at 150° C. and reaches maximumactivity around 300° C.

In the condensation/filtration zone the temperature ranges from ambientto about 150° C. The major process in this zone is thecondensation/filtration of the smoke components. Some amount of carbonmonoxide and carbon dioxide diffuse out of the cigarette and some oxygendiffuses into the cigarette. The partial pressure of oxygen in thecondensation/filtration zone does not generally recover to theatmospheric level.

According to a preferred method, the nanostructured fibrils are formedin situ by ablation and are deposited directly on tobacco cut fillerand/or cigarette paper. According to a further embodiment, thenanostructured fibrils can be deposited on the tobacco cut filler and/orcigarette paper used to form a cigarette.

The nanostructured fibrils are a class of materials whose distinguishingfeature is that their average diameter, or other structural domain sizeis below about 500 nanometers. The nanostructured fibrils can have anaverage constituent particle size less than about 100 nm, preferablyless than about 50 nm, more preferably less than about 10 nm, and mostpreferably less than about 7 nm. At this small scale, a variety ofconfinement effects can significantly change the properties of thematerial that, in turn, can lead to commercially useful characteristics.For example, nanostructured fibrils have very high surface area tovolume ratios, which makes them attractive for catalytic applications.

During the conversion of CO to CO₂, the nanostructured fibrils maybecome reduced. For example, nanostructured fibrils of Fe₂O₃ may bereduced to FeO or Fe during the reaction of CO to CO₂.

Iron oxide is a preferred constituent in the nanostructured fibrilsbecause it has a dual function as a CO catalyst in the presence ofoxygen and as a CO oxidant for the direct oxidation of CO in the absenceof oxygen. A catalyst that can also be used as an oxidant is especiallyuseful for certain applications, such as within a burning cigarettewhere the partial pressure of oxygen can be very low.

The nanostructured fibrils will preferably be distributed throughout thetobacco rod of a cigarette. By providing the nanostructured fibrilsthroughout the tobacco rod, it is possible to reduce the amount ofcarbon monoxide drawn through the cigarette, and particularly at boththe combustion region and in the pyrolysis zone.

The nanostructured fibrils, as described above, may be provided alongthe length of a tobacco rod or at discrete locations along the length ofa tobacco rod. For example, the nanostructured fibrils can be depositedon loose cut filler tobacco stock or deposited directly on a tobaccocolumn prior to wrapping cigarette paper around the cigarette column.

The amount of the nanostructured fibrils can be selected such that theamount of carbon monoxide in mainstream smoke is reduced during smokingof a cigarette. Preferably, the amount of the nanostructured fibrilswill be a catalytically effective amount, e.g., an amount sufficient tooxidize and/or catalyze at least 10% of the carbon monoxide inmainstream smoke, more preferably at least 25%.

One embodiment provides tobacco cut filler comprising nanostructuredfibrils wherein the nanostructured fibrils are formed and depositeddirectly on the tobacco cut filler by laser ablation under an appliedelectric field.

Any suitable tobacco mixture may be used for the cut filler. Examples ofsuitable types of tobacco materials include flue-cured, Burley, Md. orOriental tobaccos, the rare or specialty tobaccos, and blends thereof.The tobacco material can be provided in the form of tobacco lamina,processed tobacco materials such as volume expanded or puffed tobacco,processed tobacco stems such as cut-rolled or cut-puffed stems,reconstituted tobacco materials, or blends thereof. The tobacco can alsoinclude tobacco substitutes.

In cigarette manufacture, the tobacco is normally employed in the formof cut filler, i.e., in the form of shreds or strands cut into widthsranging from about 1/10 inch to about 1/20 inch or even 1/40 inch. Thelengths of the strands range from between about 0.25 inches to about 3.0inches. The cigarettes may further comprise one or more flavorants orother additives (e.g. burn additives, combustion modifying agents,coloring agents, binders, etc.) known in the art.

Another embodiment provides a cigarette comprising tobacco cut fillerand cigarette paper, wherein at least one of the cut filler and thecigarette paper comprises nanostructured fibrils. A further embodimentprovides a method of making a cigarette comprising (i) depositingnanostructured fibrils on at least one of tobacco cut filler andcigarette paper; (ii) providing the tobacco cut filler to a cigarettemaking machine to form a tobacco column; and (iii) placing the cigarettepaper around the tobacco column to form a tobacco rod of a cigarette.The nanostructured fibrils can be deposited on or incorporated intobacco cut filler and cigarette paper during the process of forming thenanostructured fibril. According to a further embodiment, thenanostructured fibrils can be formed and then deposited on orincorporated in tobacco cut filler and cigarette paper using techniquessuch as dusting or dry-mixing.

Techniques for cigarette manufacture are known in the art. Anyconventional or modified cigarette making technique may be used toincorporate the nanostructured fibrils. The resulting cigarettes can bemanufactured to any known specifications using standard or modifiedcigarette making techniques and equipment. Typically, the cut fillercomposition is optionally combined with other cigarette additives, andprovided to a cigarette making machine to produce a tobacco column,which is then wrapped in cigarette paper, and optionally tipped withfilters.

Cigarettes may range from about 50 mm to about 120 mm in length. Thecircumference is from about 15 mm to about 30 mm in circumference, andpreferably around 25 mm. The tobacco packing density is typicallybetween the range of about 100 mg/cm³ to about 300 mg/cm³, andpreferably 150 mg/cm³ to about 275 mg/cm³.

While various embodiments have been described, it is to be understoodthat variations and modifications may be resorted to as will be apparentto those skilled in the art. Such variations and modifications are to beconsidered within the purview and scope of the claims appended hereto.

All of the above-mentioned references are herein incorporated byreference in their entirety to the same extent as if each individualreference was specifically and individually indicated to be incorporatedherein by reference in its entirety.

What is claimed is:
 1. A method of making a cigarette, comprising: (i)depositing nanostructured fibrils on or incorporating nanostructuredfibrils in at least one of tobacco cut filler and cigarette paper,wherein said nanostructured fibrils have an aspect ratio of length towidth of greater than about 10:1, and wherein said nanostructuredfibrils comprise manganese, iron and copper, oxides and/or oxyhydroxidesof manganese, iron and copper, and mixtures thereof, or are capable ofacting as an oxidant for the conversion of carbon monoxide to carbondioxide and/or as a catalyst for the conversion of carbon monoxide tocarbon dioxide; (ii) providing the tobacco cut filler to a cigarettemaking machine to form a tobacco column; and (iii) placing the cigarettepaper around the tobacco column to form a tobacco rod of a cigarette. 2.The method of claim 1, wherein the depositing of the nanostructuredfibrils comprises: (a) depositing the nanostructured fibrils on orincorporating nanostructured fibrils in the tobacco cut filler orcigarette paper by dusting, (b) depositing the nanostructured fibrils onor incorporating nanostructured fibrils in the tobacco cut filler orcigarette paper in an amount effective to reduce the ratio in mainstreamtobacco smoke of carbon monoxide to total particulate matter by at least10%, (c) depositing the nanostructured fibrils on or incorporatingnanostructured fibrils in the tobacco cut filler or cigarette paper inan amount effective to reduce the ratio in mainstream tobacco smoke ofcarbon monoxide to total particulate matter by at least 25%, or (d)comprising depositing the nanostructured fibrils on or incorporatingnanostructured fibrils in the tobacco cut filler in an amount of lessthan about 10% by weight of the nanostructured fibrils on the tobaccocut filler.
 3. The method of claim 1, wherein the depositing orincorporating of the nanostructured fibrils comprises depositing orincorporating nanostructured fibrils having a width of less than about500 nm.
 4. The method of claim 3, wherein the nanostructured fibrilshave a width of less than 100 nm.
 5. The method of claim 4, wherein thenanostructured fibrils have a width of less than 50 nm.
 6. The method ofclaim 1, wherein the nanostructured fibrils have an aspect ratio oflength to width of greater than 1,000:1.
 7. The method of claim 6,wherein the nanostructured fibrils have an aspect ratio of length towidth of greater than about 1,000,000:1.
 8. A method of producingtobacco cut filler or cigarette paper or both, comprising: depositingnanostructured fibrils on, or incorporating nanostructured fibrils in,at least one of tobacco cut filler and cigarette paper, wherein saidnanostructured fibrils comprise manganese, iron and copper, oxidesand/or oxyhydroxides of manganese, iron and copper, and mixturesthereof, or are capable of acting as an oxidant for the conversion ofcarbon monoxide to carbon dioxide and/or as a catalyst for theconversion of carbon monoxide to carbon dioxide.